Processes for producing 2,3,3,3-tetrafluoropropene and/or 1,2,3,3-tetrafluoropropene

ABSTRACT

A process is disclosed for making CF 3 CF═CH 2  or mixtures thereof with CHF 2 CF═CHF. This process involves (a) reacting CHCl 2 CF 2 CF 3 , and optionally CHClFCF 2 CClF 2 , with H 2  in the presence of a catalytically effective amount of a hydrogenation catalyst to form CH 3 CF 2 CF 3  and, when CHClFCF 2 CClF 2  is present, CH 2 FCF 2 CHF 2 ; (b) dehydrofluorinating CH 3 CF 2 CF 3 , and optionally any CH 2 FCF 2 CHF 2 , from (a) to form a product mixture including CF 3 CF═CH 2  and, if CH 2 FCF 2 CHF 2  is present, CHF 2 CF═CHF; and optionally (c) recovering CF 3 CF═CH 2 , or a mixture thereof with CHF 2 CF═CHF from the product mixture formed in (b) and/or (d) separating at least a portion of any CHF 2 CF═CHF in the product mixture formed in (b) from the CF 3 CF═CH 2  in the product mixture formed in (b).

FIELD OF THE INVENTION

The present invention relates to processes that involve the production of halogenated hydrocarbon products comprising 2,3,3,3-tetrafluoropropene and/or 1,2,3,3-tetrafluoropropene.

BACKGROUND OF THE INVENTION

As a result of the Montreal Protocol phasing out ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs), industry has been working for the past few decades to find replacement refrigerants. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new hydrofluorocarbon refrigerants, HFC-134a (CF₃CH₂F) being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol. The production of other hydrofluorocarbons for use in applications such as solvents, blowing agents, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishants and power cycle working fluids has also been the subject of considerable interest.

There is also considerable interest in developing new refrigerants with reduced global warming potential for the mobile air-conditioning market.

2,3,3,3-Tetrafluoropropene (CH₂═CFCF₃, HFC-1234yf) and 1,2,3,3-tetrafluoropropene (CHF═CFCHF₂, HFC-1234ye), both having zero ozone depletion and low global warming potential, have been identified as a potential components in refrigerant blends (see PCT WO 2006/094303). HFC-1234yf has been prepared by reaction of CH₂ClC₂F₅ with zinc in ethanol as reported by Haszeldine and Steele in Journal of the Chemical Society, pages 2193-2197 (1957). HFC-1234ye has been prepared as a by-product in the vapor phase fluorination of 3-chloro-1,1,2,2-tetrafluoropropane over a chromium catalysts as disclosed by Yasuhara, et. al. in U.S. Pat. No. 5,629,461. There is a need for new manufacturing processes for the production of HFC-1234yf and HFC-1234ye.

SUMMARY OF THE INVENTION

The present invention provides a process for making HFC-1234yf or mixtures thereof with HFC-1234ye. This process comprises (a) reacting HCFC-225ca (CHCl₂CF₂CF₃) and optionally HCFC-225cb (CHClFCF₂CClF₂) with H₂ in the presence of a catalytically effective amount of a hydrogenation catalyst to form CH₃CF₂CF₃ (HFC-245cb) and, when HCFC-225cb is present, CH₂FCF₂CHF₂ (HFC-245ca); (b) dehydrofluorinating HFC-245cb, and optionally any HFC-245ca, from (a) to form a product mixture comprising HFC-1234yf and, if HFC-245ca is present, HFC-1234ye; and optionally (c) recovering HFC-1234yf, or a mixture thereof with HFC-1234ye, from the product mixture formed in (b); and optionally (d) separating at least a portion of any HFC-1234ye in the product mixture formed in (b) from the HFC-1234yf in the product mixture formed in (b).

DETAILED DESCRIPTION

The present invention provides a process for making HFC-1234yf or mixtures thereof with HFC-1234ye. HFC-1234ye may exist as one of two configurational isomers, E- or Z-. HFC-1234ye as used herein refers to either E-HFC-1234ye (CAS Reg No. [115781-19-6]) or Z-HFC-1234ye (CAS Reg. No. [730993-62-1]), as well as any combination or mixture of such isomers.

The process comprises (a) reacting C₃HCl₂F₅ with H₂ in a reaction zone in the presence of a catalytically effective amount of hydrogenation catalyst to form C₃H₃F₅ (that is, the total of HFC-245cb and any HFC-245ca); and (b) dehydrofluorinating C₃H₃F₅ from (a) to form HFC-1234. In step (a) of this process of the invention, C₃HCl₂F₅ is reacted with hydrogen in the presence of a hydrogenation catalyst. Hydrogenation catalysts suitable for use in this invention include catalysts comprising at least one catalytic metal component selected from the group consisting of iron, cobalt, rhodium, nickel, palladium, and platinum. Said catalytic metal component is typically supported on a carbonaceous carrier such as activated carbon or graphite.

Of note are embodiments wherein the C₃HCl₂F₅ component (that is, the total of HCFC-225ca and HCFC-225cb) reacted with hydrogen is primarily HCFC-225ca.

Mixtures of HCFC-225ca and HCFC-225cb can be prepared by the reaction of dichlorofluoromethane (HCFC-21) with tetrafluoroethylene (TFE) in the presence of aluminum chloride as reported by Paleta, et. al. in Collections of Czechoslovia Chemical Communications, Vol. 36, pages 1867 to 1875 (1971) or by the reaction of dichlorofluoromethane (HCFC-21) with tetrafluoroethylene (TFE) in the presence of aluminum chlorofluoride as disclosed by Sievert, et. al. in U.S. Pat. No. 5,157,171.

Catalysts suitable for the hydrogenation step include those comprising palladium, optionally together with additional Group VIII metals (e.g., Pt, Ru, Rh or Ni). The palladium may be supported on alumina, fluorided alumina, aluminum fluoride or a mixture thereof; or may be supported on carbon. The palladium-containing precursor used to prepare the catalyst is preferably a palladium salt (e.g., palladium chloride). Other metals, when used, may be added to the support during the preparation of the catalyst.

The supported metal catalysts may be prepared by conventional methods known in the art such as by impregnation of the carrier with a soluble salt of the catalytic metal (e.g., palladium chloride or rhodium nitrate) as described by Satterfield on page 95 of Heterogenous Catalysis in Industrial Practice, 2^(nd) edition (McGraw-Hill, New York, 1991). Palladium supported on alumina is available commercially. Another suitable procedure for preparing a catalyst containing palladium on fluorided alumina is described in U.S. Pat. No. 4,873,381, which is incorporated herein by reference.

By a catalytically effective amount is meant the concentration of catalysts on the support that is sufficient to carry out the catalytic reaction. The concentration of palladium on the support is typically in the range of from about 0.1% to about 10% by weight based on the total weight of the catalyst and is preferably in the range of about 0.1% to about 5% by weight based on the total weight of the catalyst. The concentration of the additional Group VIII metal, when used, is about 3% by weight, or less, based on the total weight of the catalyst; but palladium is ordinarily at least 50% by weight based on the weight of the total metals present on the support, and preferably at least 80% by weight based on the weight of the total metals present on the support.

Of note are carbon-supported catalysts in which the carbon support has been washed with acid and has an ash content below about 0.1% by weight. Hydrogenation catalysts supported on low ash carbon are described in U.S. Pat. No. 5,136,113, the teachings of which are incorporated herein by reference. Of particular note are palladium catalysts supported on carbon (see e.g., U.S. Pat. No. 5,523,501, the teachings of which are incorporated herein by reference). Also of particular note are palladium catalysts supported on three-dimensional matrix porous carbonaceous materials. Preparation of such three-dimensional matrix porous carbonaceous materials is disclosed in U.S. Pat. No. 4,978,649, incorporated herein by reference.

The relative amount of hydrogen contacted with C₃HCl₂F₅ is typically from about one mole of hydrogen per mole of C₃HCl₂F₅ to about 15 moles of H₂ per mole of the C₃HCl₂F₅ starting material. Suitable reaction temperatures are typically from about 100° C. to about 350° C., preferably from about 200° C. to about 350° C. The contact time is typically from about 1 to about 450 seconds, preferably from about 10 to about 120 seconds. The reactions are typically conducted at atmospheric pressure or superatmospheric pressure.

The effluent from the reaction zone used for step (a) typically includes HCl, unreacted hydrogen, HFC-245cb, and one or more of CFC-1214ya and HCFC-235cb (normally HCFC-235cb without significant CFC-1214ya). The effluent may also contain HFC-1234yf, and HFC-263fb. If HCFC-225cb is present as a starting material, the effluent from the reaction zone typically also includes HFC-245ca and one or more of CH₂FCF₂CClF₂ (HCFC-235cc), HCFC-235ca, and CFC-1214yb (normally HCFC-235cc and HCFC-235ca without significant CFC-1214yb).

In one embodiment of the invention, the HFC-245cb is isolated by separation processes known in the art such as distillation; and the isolated HFC-245cb, essentially free of HFC-245ca, is then used for step (b) of the process to prepare HFC-1234yf. Unreacted C₃HCl₂F₅ and intermediate products such as C₃H₂CIF₅ isomers may be recycled to step (a) of the process. Reaction by-products such as C₃Cl₂F₄ isomers may be recovered and converted to HFC-1234 in the reaction zone of step (a) of the process or separately by contact with hydrogen in the presence of a hydrogenation catalyst.

In another embodiment of the invention, the C₃HCl₂F₅ is reacted with hydrogen in the presence of catalyst in a molar ratio of H₂ to C₃HCl₂F₅ of from about 1:1 to about 15:1; and, after separation of hydrogen chloride and any hydrogen, the remaining effluent from the reaction zone is then sent directly to step (b) of the process.

In step (b) of the process of the invention, the C₃H₃F₅ produced in step (a) is contacted with a dehydrofluorination catalyst in a reaction zone for time sufficient to convert at least a portion of the C₃H₃F₅ to HFC-1234yf and, if HFC-245ca is fed to the reaction zone, HFC-1234ye. The dehydrofluorination reaction may be conducted in a tubular reactor in the vapor phase at temperatures of from about 200° C. to about 500° C. and preferably from about 300° C. to about 450° C. The contact time is typically from about 1 to about 450 seconds, preferably from about 10 to about 120 seconds.

The reaction pressure can be subatmospheric, atmospheric or superatmospheric. Generally, near atmospheric pressures are preferred. However, the dehydrofluorination of C₃H₃F₅ can be beneficially run under reduced pressure (i.e., pressures less than one atmosphere).

The catalytic dehydrofluorination can optionally be carried out in the presence of an inert gas such as nitrogen, helium or argon. The addition of an inert gas can be used to increase the extent of dehydrofluorination. Of note are processes where the mole ratio of inert gas to C₃H₃F₅ is from about 5:1 to 1:1. Nitrogen is the preferred inert gas.

Typical dehydrofluorination reaction conditions and dehydrofluorination catalysts are disclosed in U.S. Pat. No. 5,396,000, which is herein incorporated by reference in its entirety. Preferably, the dehydrofluorination catalyst comprises at least one catalyst selected from the group consisting of carbon, aluminum fluoride, fluorided alumina, and trivalent chromium oxide.

Other dehydrofluorination catalysts useful for converting C₃H₃F₅ from step (a) to HFC-1234 products are described in U.S. Pat. No. 6,093,859; the teachings of this disclosure are incorporated herein by reference. Still other dehydrofluorination catalysts suitable for use in step (b) are described in U.S. Pat. No. 6,369,284; the teachings of this disclosure are incorporated herein by reference.

The products from the step (b) reaction zone typically include HF, HFC-1234yf, and when HFC-245ca is present, the E- and Z-forms of HFC-1234ye. Unconverted C₃H₃F₅ may be recovered and recycled back to the dehydrofluorination reactor to produce additional quantities of HFC-1234. The separation steps involving recovery of HFC-1234yf and/or HFC-1234ye, such as steps (c) and (d) above, can be carried out using conventional separation technology such as distillation.

Of note are processes wherein in step (a), the C₃HCl₂F₅ contacted with H₂ includes HCFC-225cb; wherein the C₃H₃F₅ dehydrofluorinated in (b) includes HFC-245ca; and wherein the product mixture formed in (b) includes HFC-1234ye. Included are processes wherein HFC-1234yf essentially free of HFC-1234ye is recovered and/or HFC-1234ye essentially free of HFC-1234yf is recovered.

Also of note are embodiments where HFC-1234yf is a desired product, and is recovered from the product mixture of step (b). The HFC-1234yf present in the effluent from the reaction zone may be separated from the other components of the product mixture and unreacted starting materials by conventional means (e.g., distillation). When HF is present in the effluent, this separation can also include isolation of azeotrope or near azeotrope composition of HFC-1234yf and HF and further processing to produce HF-free HFC-1234yf by using procedures similar to that disclosed in U.S. Patent Application No. 2006/0106263, which is incorporated herein by reference.

The reactor, distillation columns, and their associated feed lines, effluent lines, and associated units used in applying the process of this invention should be constructed of materials resistant to hydrogen fluoride and hydrogen chloride. Typical materials of construction, well-known to the fluorination art, include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.

EXAMPLES

LEGEND 225ca is CF₃CF₂CHCl₂ 225cb is CClF₂CF₂CHClF 235ca is CHClFCF₂CHF₂ 235cb is CH₂ClCF₂CF₃ 235cc is CH₂FCF₂CClF₂ 245ca is CHF₂CF₂CH₂F 245cb is CF₃CF₂CH₃ 254eb is CF₃CHFCH₃ 263fb is CF₃CH₂CH₃ 1214ya is CF₃CF═CCl₂ 1214yb is CClF₂CF═CClF 1234ye is CHF₂CF═CHF 1234yf is CF₃CF═CH₂

Example 1 Synthesis of CF₃CF═CH₂ by Dehydrofluorination with Fluorided Alumina Catalyst

A Hastelloy™ tube reactor (2.54 cm OD×2.17 cm ID×24.1 cm L) was filled with 25 cc of gamma-alumina ground to 12-20 mesh (0.84 to 1.68 mm). The catalyst was activated by heating at 200° C. for 15 minutes under a nitrogen purge and then reacted with a HF/N₂ mixture heated up to 425° C. to yield 16.7 gm of activated fluorided alumina.

At a temperature of 350° C., 10 sccm of nitrogen (1.7×10⁻⁷ m³/s) and 15 sccm (2.5×10⁻⁷ m³/s) of CF₃CF₂CH₃ were mixed and flowed through the reactor. The temperature was then raised to 400° C., the flow rates held constant. The effluent for both temperatures was sampled and analyzed by ¹⁹F NMR. Additionally, the effluent was analyzed by GC to determine concentrations as listed in Table 1.

TABLE 1 CF₃CF₂CH₃ Temp., N₂ flow flow Concentrations, (Mole %) ° C. (sccm) (sccm) CF₃CF═CH₂ CF₃CF₂CH₃ Unks 350 10 15 84.2 12.8 3.0 400 10 15 91.3 1.9 6.8 Unks = unknowns

Example 2 Synthesis of CF₃CF═CH₂ with Carbon Catalyst

A Hastelloy™ tube reactor (2.54 cm OD×2.17 cm ID×24.1 cm L) was filled with 25 cc (14.32 g) of Sibunit2 carbon beads. The catalyst was activated by heating at about 300° C. under a nitrogen purge.

Following the procedure of Example 1, a mixture of 10 sccm (1.7×10⁻⁷ m³/s) of nitrogen and 15 sccm (2.5×10⁻⁷ m³/s) of CF₃CF₂CH₃ were passed through the reactor giving a contact time of 60 seconds. The flows were reduced to 5 sccm (8.3×10⁻⁸ m³/s) of nitrogen and 7.5 sccm (1.3×10⁻⁷ m³/s) of CF₃CF₂CH₃ giving a contact time of 120 seconds. The effluent was sampled under both sets of conditions and analyzed by ¹⁹F NMR. The effluent compositions as determined by GC are listed in Table 2.

TABLE 2 CF₃CF₂CH₃ Temp., N₂ flow flow Concentrations, Mole % ° C. (sccm) (sccm) CF₃CF═CH₂ CF₃CF₂CH₃ Unks 400 10 15 6.0 93.9 0.1 400 5 7.5 22.8 76.4 0.8 Unks = unknowns

Example 3 Synthesis of CHF₂CF═CHF from CHF₂CF₂CH₂F

A 0.375 inch (0.95 cm) O.D. Hastelloy™ nickel alloy tube was charged with 7.0 grams (10 cc) of gamma-alumina ground to 12/20 mesh (0.84 to 1.68 mm). The tube was purged with nitrogen (50 sccm, 8.3×10⁻⁷ m³/s) for twenty minutes as the temperature was raised from 40° C. to 175° C. The nitrogen flow was continued as anhydrous hydrogen fluoride (50 sccm, 8.3×10⁻⁷ m³/s) was added to the reactor for about 1.5 hours. The nitrogen flow was then reduced to 20 sccm (3.3×10⁻⁷ m³/s) and the hydrogen fluoride flow increased to 80 sccm (1.3×10⁻⁶ m³/s) as the temperature in the tube was increased from 174° C. to 373° C. over the course of 3.7 hours. The nitrogen flow was then reduced to 10 sccm (1.7×10⁻⁷ m³/s) and the hydrogen fluoride flow was maintained at 80 sccm (1.3×10⁻⁶ m³/s) for one hour at 400° C. The reactor temperature was then adjusted to 290° C. and the reactor purged with nitrogen.

CHF₂CF₂CH₂F was vaporized and fed to the reactor at such a rate as to maintain a contact time with the catalyst of 120 seconds. No nitrogen co-feed was present. Gas chromatographic analyses of the reactor effluent at three temperatures are listed in Table 3.

TABLE 3 GC Area Percent Reactor E and Z- Temp, ° C. CHF₂CF₂CH₂F CHF₂CHFCHF₂ CHF₂CF═CHF 275 72.3 5.5 22.0 325 40.8 6.9 51.7 375 27.0 3.2 68.9

Example 4 Hydrogenation of CHCl₂CF₂CF₃ and CHClFCF₂CClF₂

A commercial palladium on aluminum oxide catalyst (0.5% Pd/Al₂O₃, 10 cc, 12-20 mesh (1.68-0.84 mm)) was placed in a 30.5 cm×1.27 cm o.d. Hastelloy® tube. The tube was connected to a reactor system and surrounded with a electrically-heated furnace. The catalyst was first purged with nitrogen (25 sccm, 4.1×10⁻⁷ m³/s) for three hours as the temperature of the reactor was increased from 100° C. to 300° C. After cooling to 150° C., the catalyst was reduced with hydrogen (20 sccm, 3.3×10⁻⁷ m³/s) for three hours as the temperature of the reactor was increased from 100° C. to 300° C. After again cooling to 150° C. under a nitrogen purge, the catalyst was treated with a mixture of nitrogen and hydrogen fluoride according to the following sequence (flow rate N₂, flow rate H₂, time, temperature): 45 sccm (7.4×10⁻⁷ m³/s), 5 sccm (8.3×10⁻⁸ m³/s), 2 hours, 150° C.; 40 sccm (6.6×10⁻⁷ m³/s), 10 sccm (1.7×10⁻⁷ m³/s), 2 hours, 150° C.; 40 sccm (6.6×10⁻⁷ m³/s), 10 sccm (1.7×10⁻⁷ m³/s), 2 hours, 200° C.; 40 sccm (6.6×10⁻⁷ m³/s), 10 sccm (1.7×10⁻⁷ m³/s), 2 hours, 250° C.; 25 sccm (4.1×10⁻⁷ m³/s), 25 sccm (4.1×10⁻⁷ m³/s), 2 hours, 250° C. The flow of HF was then stopped and the catalyst purged with nitrogen (20 sccm, (3.3×10⁻⁷ m³/s) as the temperature was reduced to about 150° C. The catalyst was then used for several runs involving reactions with hydrogen and/or hydrogen fluoride and then reactivated by treatment with air (40 sccm (6.6×10⁻⁷ m³/s) for 2 hours at 300° C.) followed by nitrogen purging, treatment with hydrogen (50 sccm (8.3×10⁻⁷ m³/s) for 2 hours at 350° C.) and another nitrogen purging.

A mixture of HCFC-225 isomers comprising CF₃CF₂CHCl₂ (HCFC-225ca, about 41%) and CClF₂CF₂CHClF (HCFC-225cb, about 59%) and hydrogen (1:3 molar ratio) was fed to the above catalyst at 300° C.; the contact time was nominally 30 seconds. The analysis of the reactor effluent as determined by GC-MS is given in TABLE 4.

Example 5 Hydrogenation of HCFC-225's

A mixture of HCFC-225 isomers and hydrogen (1:5 molar ratio) was fed to the catalyst described in Example No. 4 at 350° C.; the contact time was nominally 20 seconds. The analysis of the reactor effluent as determined by GC-MS is given in TABLE 4.

TABLE 4 GC area percent EX. HFC- HFC- HFC- HFC- HFC- HCFC- HCFC- HCFC- HCFC- NO. 245cb 1234yf 263fb 254eb 245ca 235cc 235cb 235ca 225ca/cb 4 41.1 0.1 0.8 0.7 1.5 14.5 8.8 4.4 26.5 5 31.4 0.6 3.9 1.6 1.0 8.0 7.3 2.8 40.4 

1. A process for making CF₃CF═CH₂ or mixtures thereof with CHF₂CF═CHF, comprising: (a) reacting CHCl₂CF₂CF₃, and optionally CHClFCF₂CClF₂, with H₂ in the presence of a catalytically effective amount of a hydrogenation catalyst to form CH₃CF₂CF₃ and, if CHClFCF₂CClF₂ is present, CH₂FCF₂CHF₂; (b) dehydrofluorinating CH₃CF₂CF₃, and optionally any CH₂FCF₂CHF₂, from (a) to form a product mixture comprising CF₃CF═CH₂ and, when CH₂FCF₂CHF₂ is present, CHF₂CF═CHF; and optionally (c) recovering CF₃CF═CH₂, or a mixture thereof with CHF₂CF═CHF, from the product mixture formed in (b); and optionally (d) separating at least a portion of any CHF₂CF═CHF in the product mixture formed in (b) from the CF₃CF═CH₂ in the product mixture formed in (b).
 2. The process of claim 1 wherein the C₃HCl₂F₅ contacted with H₂ includes CHClFCF₂CClF₂; wherein the CH₂FCF₂CHF₂ produced in (a) is separated from CH₃CF₂CF₃ produced in (a); and wherein the C₃H₃F₅ dehydrofluorinated in (b) is essentially free of CH₂FCF₂CHF₂.
 3. The process of claim 2 wherein the C₃HCl₂F₅ contacted with H₂ includes CHClFCF₂CClF₂; wherein the C₃H₃F₅ dehydrofluorinated in (b) includes CH₂FCF₂CHF₂; and wherein the product mixture formed in (b) includes CHF₂CF═CHF.
 4. The process of claim 3 wherein CF₃CF═CH₂ essentially free of CHF₂CF═CHF is recovered.
 5. The process of claim 3 wherein CHF₂CF═CHF essentially free of CF₃CF═CH₂ is recovered.
 6. The process of claim 1 wherein the hydrogenation catalyst used in (a) comprises palladium supported on a three-dimensional matrix porous carbonaceous material.
 7. The process of claim 1 wherein the hydrogenation catalyst used in (a) comprises palladium supported on alumina, fluorided alumina, aluminum fluoride or a mixture thereof. 